U.S. patent number 9,272,560 [Application Number 14/346,895] was granted by the patent office on 2016-03-01 for thermal transfer sheet.
This patent grant is currently assigned to DAI NIPPON PRINTING CO., LTD.. The grantee listed for this patent is DAI NIPPON PRINTING CO., LTD. Invention is credited to Yoshimasa Kobayashi, Kano Sakamoto, Tomoko Suzuki.
United States Patent |
9,272,560 |
Suzuki , et al. |
March 1, 2016 |
Thermal transfer sheet
Abstract
Provided is a thermal transfer sheet capable of repressing
residue that accumulates before insertion of a heating element of
the thermal head. In the thermal transfer sheet, a heat-resistant
lubricating layer is formed on a surface of the substrate, wherein
the heat-resistant lubricating layer includes one or more of layers
which include a back face layer, the back face layer is arranged at
a position farthest from the substrate, at least one layer which
composes the heat-resistant lubricating layer includes a binder
resin and organic minute particles which each has a polygonal
shape, and a portion of surfaces of the organic minute particles
protrude from a surface of the back layer.
Inventors: |
Suzuki; Tomoko (Tokyo,
JP), Kobayashi; Yoshimasa (Tokyo, JP),
Sakamoto; Kano (Tokyo, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
DAI NIPPON PRINTING CO., LTD |
Tokyo |
N/A |
JP |
|
|
Assignee: |
DAI NIPPON PRINTING CO., LTD.
(Tokyo, JP)
|
Family
ID: |
47995590 |
Appl.
No.: |
14/346,895 |
Filed: |
September 26, 2012 |
PCT
Filed: |
September 26, 2012 |
PCT No.: |
PCT/JP2012/074648 |
371(c)(1),(2),(4) Date: |
March 24, 2014 |
PCT
Pub. No.: |
WO2013/047560 |
PCT
Pub. Date: |
April 04, 2013 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
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US 20140212604 A1 |
Jul 31, 2014 |
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Foreign Application Priority Data
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|
|
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Sep 30, 2011 [JP] |
|
|
2011-218137 |
Sep 12, 2012 [JP] |
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2012-201010 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B41M
5/44 (20130101); B32B 5/16 (20130101); B41M
5/42 (20130101); B41M 2205/04 (20130101); B41M
2205/36 (20130101); B41M 2205/02 (20130101); B41M
2205/34 (20130101) |
Current International
Class: |
B41M
5/42 (20060101); B32B 5/16 (20060101); B41M
5/44 (20060101) |
Field of
Search: |
;503/227
;428/32.64,32.66,331 |
Foreign Patent Documents
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|
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07-329439 |
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Dec 1995 |
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JP |
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10-138649 |
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May 1998 |
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JP |
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2005-119154 |
|
May 2005 |
|
JP |
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2007-307764 |
|
Nov 2007 |
|
JP |
|
Other References
International Search Report, PCT/JP2012/074648, Oct. 23, 2012.
cited by applicant.
|
Primary Examiner: Hess; Bruce H
Attorney, Agent or Firm: Young & Thompson
Claims
The invention claimed is:
1. A thermal transfer sheet comprising a heat-resistant lubricating
layer formed on a surface of a substrate, the lubricating layer
comprising a back face portion arranged as an outermost layer of
the lubricating layer, the lubricating layer comprising a binder
resin and organic minute particles having a polygonal shape,
wherein a portion of the surface of the organic minute particles
protrudes from an outermost surface of the back face portion.
2. The thermal transfer sheet according to claim 1, wherein the
organic minute particles are silicone resin minute particles.
3. The thermal transfer sheet according to claim 1, wherein the
organic minute particles have an average particle diameter of 0.3
.mu.m to 15 .mu.m.
4. The thermal transfer sheet according to claim 1, wherein the
binder resin is a cured resin in which one or both of polyvinyl
butyral resin and polyvinyl acetal resin was cured by an isocyanate
curing agent, and a molar equivalent ratio of hydroxyl groups
included in the one or both of the polyvinyl butyral resin and
polyvinyl acetal resin and isocyanate groups of the isocyanate
curing agent (--NCO/--OH) is 0.01 to 0.7.
5. The thermal transfer sheet according to claim 1, further
comprising at least one of a color material layer and a
transcriptive protective layer, provided on another surface of the
substrate.
6. A thermal transfer sheet comprising a heat-resistant lubricating
layer formed on a surface of a substrate, the heat-resistant
lubricating layer comprising one or more layers which includes a
back face layer, the back face layer being arranged as an outermost
layer of the lubricating layer, the lubricating layer comprising a
binder resin, wherein the back face layer comprises organic minute
particles having a polygonal shape, and a portion of the surface of
the organic minute particles protrudes from an outermost surface of
the back face portion.
7. The thermal transfer sheet according to claim 6, wherein the
organic minute particles are silicone resin minute particles.
8. The thermal transfer sheet according to claim 6, wherein the
organic minute particles have an average particle diameter of 0.3
.mu.m to 15 .mu.m.
9. The thermal transfer sheet according to claim 6, wherein the
binder resin is a cured resin in which one or both of polyvinyl
butyral resin and polyvinyl acetal resin was cured by an isocyanate
curing agent, and a molar equivalent ratio of hydroxyl groups
included in the one or both of the polyvinyl butyral resin and
polyvinyl acetal resin and isocyanate groups of the isocyanate
curing agent (--NCO/--OH) is 0.01 to 0.7.
10. The thermal transfer sheet according to claim 6, further
comprising at least one of a color material layer and a
transcriptive protective layer, provided on another surface of the
substrate.
11. The thermal transfer sheet according to claim 6, wherein
heat-resistant lubricating layer comprises a primer layer arranged
between the substrate and the back face layer, the primer layer
comprising a binder resin.
12. The thermal transfer sheet according to claim 11, wherein the
primer layer comprises one or more of a curing agent, an adhesion
promoter, and an antistatic agent.
13. The thermal transfer sheet according to claim 11, wherein the
back face layer comprises 0.01 to 3% by weight of the organic
minute particles based on total solid content of the back face
layer.
14. A thermal transfer sheet comprising a heat-resistant
lubricating layer formed on a surface of a substrate, the
heat-resistant lubricating layer comprising one or more layers
which includes a back face layer, the back face layer being
arranged as an outermost layer of the heat-resistant lubricating
layer, the heat-resistant lubricating layer comprising a binder
resin, wherein the heat-resistant lubricating layer comprises
organic minute particles having a polygonal shape, and a portion of
the surface of the organic minute particles protrudes from an
outermost surface of the back face portion.
15. The thermal transfer sheet according to claim 14, wherein the
organic minute particles are silicone resin minute particles.
16. The thermal transfer sheet according to claim 14, wherein the
organic minute particles have an average particle diameter of 0.3
.mu.m to 15 .mu.m.
17. The thermal transfer sheet according to claim 14, wherein the
binder resin is a cured resin in which one or both of polyvinyl
butyral resin and polyvinyl acetal resin was cured by an isocyanate
curing agent, and a molar equivalent ratio of hydroxyl groups
included in the one or both of the polyvinyl butyral resin and
polyvinyl acetal resin and isocyanate groups of the isocyanate
curing agent (--NCO/--OH) is 0.01 to 0.7.
18. The thermal transfer sheet according to claim 14, further
comprising at least one of a color material layer and a
transcriptive protective layer, provided on another surface of the
substrate.
19. The thermal transfer sheet according to claim 14, wherein the
heat-resistant lubricating layer comprises a primer layer arranged
between the substrate and the back face layer, the primer layer
comprising a binder resin.
20. The thermal transfer sheet according to claim 19, wherein the
primer layer comprises one or more of a curing agent, an adhesion
promoter, and an antistatic agent.
21. The thermal transfer sheet according to claim 19, wherein the
organic minute particles are at least partially contained in the
primer layer.
22. The thermal transfer sheet according to claim 21, wherein the
heat-resistant lubricating layer comprises 0.01 to 3% by weight of
the organic minute particles based on total solid content of the
primer layer.
Description
TECHNICAL FIELD
This invention relates to a thermal transfer sheet, and more
particularly, the present invention relates to a thermal transfer
sheet which is capable of repressing generation of residue that
will accumulate around a heating element of a thermal head, and
which can avoid wear of the thermal head.
BACKGROUND ART
Currently, sublimation type thermal transfer recording method is
known, in which a thermal transfer sheet comprising a colorant
layer provided on one side of a substrate such as polyester film,
the color layer comprising sublimation type dyes supported by a
suitable binder is superposed on an image-receiving article, then
another side of the substrate is allowed to be in contact with a
thermal head so as to perform heat treatment by the thermal head,
and thereby the sublimation type dyes are transferred to the
image-receiving article. According to the sublimation type thermal
transfer recording method, since it is possible to control the
transferring amount of the sublimation type dye dot unit by dot
unit with varying the amount of energy applied to the thermal
transfer sheet, it is possible to perform a density gradation.
Therefore, this method can provide a high quality image which is
very vivid, and excels in the transparency, and the color
reproducibility and the gradient of halftones, and which is
comparable to full-color photograph image.
Incidentally, with respect to the thermal transfer sheet, when the
printing is performed by contacting directly the thermal head
directly to the substrate, a probable case that a sticking is
caused by a frictional force generated between the substrate and
the thermal head will arise, and this will result in printing
failure. Further, there is a possibility that the substrate is
fused to the thermal head by the heat during printing, and this
fusion will prevent the travel of the thermal transfer sheet. As
results, not only the sticking, but also the fracture of the sheet
may arise in extreme cases. Accordingly, in the field of thermal
transfer sheet, a backing layer which is provided on the other
surface of the substrate for the purpose of improving the thermal
resistance and giving the driving stability by imparting lubricity
is usually adopted.
However, with respect to the backing layer for the purpose of
driving stability, a problem that the residue derived from the
components of the backing layer is accumulated around the heating
element of the thermal head during the thermal transfer is
inherent. If the residue is attached to the thermal head, there is
a probably case that the heat from the thermal head will be not
transmitted sufficiently to the thermal transfer sheet, and thus
the formation of high-quality image can not be attained, and there
is also a case that printing flaws due to the residue that has
accumulated occurs. Further, in a printing condition where a
concentrated solid printing portion and a gradation pattern portion
of halftone are adjacent to each other among many printing
conditions, when the heating energy applied to the thermal head is
rapidly changed from the high level to the low level, a problem
which seems to be the influence of residue that has been
accumulated at the contact portion between the thermal head and the
back face side of the thermal transfer sheet, and in which a dirt
tailing (inconsistencies in density) arises in the gradation
pattern portion of the halftone, will arise. Therefore, in the
field of thermal transfer sheet, to prevent the residue of the
backing layer attaching to the thermal head, or to prevent the
attached residue accumulating to the thermal head, has become an
important subject.
Under such a circumstance, for instance, in Patent Literature 1, a
thermal transfer sheet which is provided with a back face layer
containing an organic filler is disclosed. According to the thermal
transfer sheet disclosed in the Patent Literature 1, there is no
adhesion of residue to the thermal head, and it does not cause
faulty transfer of the transcriptive protective layer. Further, in
addition to this literature, various thermal transfer sheets each
back face layer of which contains minute particles for removing the
residue attached to the thermal head have also been proposed.
PRIOR ART DOCUMENT
Patent Literature
Patent Literature 1: JP 2007-307764 A
SUMMARY OF INVENTION
Problem to be Solved by the Invention
However, it is difficult, for the thermal transfer sheet which
comprises a back face layer as disclosed in the Patent Literature
1, and the thermal transfer sheets which have been proposed to
date, to satisfy both of a repressive effect to the attaching of
the residue to the thermal head and a preventing effect to the
wearing of the thermal head. Further, with respect to the shape of
the organic filler contained in the back face layer of the Patent
Literature 1, it can not be said that the performance for scraping
the residue attached to the thermal head is sufficient. Therefore,
not only the kind of component contained in the back face layer,
but also its shape should also be considered.
The present invention is the one contrived in such a situation, and
a main purpose of the present invention is to provide a thermal
transfer sheet which can satisfy both of a repressive effect to the
attaching of the residue to the thermal head and a preventing
effect to the wearing of the thermal head, and which is capable of
maintaining these effects for a long time.
Means for Solving the Problem
The present invention for solving the above mentioned problem is a
thermal transfer sheet in which a heat-resistant lubricating layer
is formed on a surface of the substrate, wherein the heat-resistant
lubricating layer comprises one or more of layers which include a
back face layer; wherein the back face layer is arranged at a
position farthest from the substrate in the case that the
heat-resistant lubricating layer comprises two or more of the
layers; wherein at least one layer which composes the
heat-resistant lubricating layer comprises a binder resin and
organic minute particles which each has a polygonal shape; and
wherein a portion of surfaces of the organic minute particles
protrude from a surface of the back layer.
Further, the organic minute particles may be silicone resin minute
particles. An average particle diameter of the organic minute
particles in the case of the organic minute particles are contained
in the back face layer may be not less than 0.3 .mu.m and not more
than 15 .mu.m.
Further, the binder resin contained in the back face layer may be a
cured resin in which one or both of polyvinyl butyral resin and
polyvinyl acetal resin was cured by an isocyanate curing agent, and
a molar equivalent ratio of hydroxyl groups included in one or both
of polyvinyl butyral resin and polyvinyl acetal resin and
isocyanate groups of the isocyanate curing agent, (--NCO/--OH), may
be not less than 0.01 and less than 0.7.
Effect of the Invention
According to the thermal transfer sheet of the present invention,
it is possible to provide a thermal transfer sheet which can
satisfy both of the repressive effect to the attaching of the
residue to the thermal head and the preventing effect to the
wearing of the thermal head, and which is capable of maintaining
these effects for a long time. Further, according to one embodiment
of the thermal transfer sheet of the present invention, it is
possible to realize full performance desired for the back face
layer by adjusting cross-linking density of the back face
layer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of a first embodiment.
FIG. 2 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of the first embodiment.
FIG. 3 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of the first embodiment.
FIG. 4 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of the first embodiment.
FIG. 5 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of a second embodiment.
FIG. 6 is a schematic sectional view showing an example of the
thermal transfer sheet of the present invention which comprises a
heat-resistant lubricating layer of the second embodiment.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
Hereinafter, the thermal transfer sheet 10 according to the present
invention will be described concretely with reference to drawings.
As shown in FIGS. 1-6, the thermal transfer sheet 10 of the present
invention is a thermal transfer sheet in which a heat-resistant
lubricating layer 7 is formed on a surface of the substrate 1,
wherein the heat-resistant lubricating layer 7 comprises one or
more of layers which include a back face layer 5; wherein the back
face layer 5 is arranged at a position farthest from the substrate
in the case that the heat-resistant lubricating layer 7 comprises
two or more of the layers; wherein at least one layer which
composes the heat-resistant lubricating layer 7 comprises a binder
resin and organic minute particles which each has a polygonal
shape; and wherein a portion of surfaces of the organic minute
particles protrude from a surface of the back layer.
FIGS. 1-4 are schematic sectional views each showing an example of
the thermal transfer sheet 10 of the present invention in which the
polygonal shaped organic minute particles 20 are included in the
back face layer 5 which constitutes the heat-resistant lubricating
layer 7 and a portion of surfaces of the organic minute particles
protrude from a surface of the back face layer 5, in other words,
are schematic sectional views each showing an example of the
thermal transfer sheet 10 of the present invention which has a
heat-resistant lubricating layer 7 of a first embodiment. In FIGS.
1 and 2, examples in which the heat-resistant lubricating layer 7
is constituted only by the back face layer 5 are illustrated, and
in FIGS. 3 and 4, examples in which the heat-resistant lubricating
layer 7 is constituted by two or more layers including the back
face layer 5.
FIGS. 5 and 6 are schematic sectional views each showing an example
of the thermal transfer sheet 10 of the present invention in which
the heat-resistant lubricating layer 7 is constituted by two or
more layers including the back face layer 5, the polygonal shaped
organic minute particles 20 are contained in the layer(s) other
than the back face layer 5 in the aforementioned two or more
layers, and a portion of surfaces of the organic minute particles
20 which contained in the layer (s) other than the back face layer
5 protrude from a surface of the back face layer 5, in other words,
are schematic sectional views each showing an example of the
thermal transfer sheet 10 of the present invention which has a
heat-resistant lubricating layer of a second embodiment.
In the thermal transfer sheets of the embodiments shown in FIGS. 1,
3, and 5, a transcriptive protective layer 3 is provided on the
other surface of the substrate 1, and in the thermal transfer sheet
of the embodiments shown in FIGS. 2, 4, and 6, a color material
layer 4 is provided on the other side of the substrate 1. Herein,
the transfer protective layer 3, the color material layer 4, a
primer layer 6, and a releasing layer 2 shown in FIGS. 1-6 are
optional components of the thermal transfer sheet 10 of the present
invention.
Hereinafter, the thermal transfer sheet 10 of the present invention
will be described in further detail with reference to the
drawings.
(Substrate)
The substrate 1 is an essential component of the thermal transfer
sheet 10 of the present invention, and it is provided for the
purpose of supporting the color material layer 4 or the
transcriptive protective layer 3 and the heat-resistant lubricating
layer 7 which includes the back face layer 5. Although the material
for the substrate 1 is not particularly limited, but it is
preferable that the material can withstand the heat applied by the
thermal head in transferring the dyestuffs of the color material
layer 4 or the transcriptive protective layer 3 onto a
transcription receiving article, and has a mechanical strength
which brings no harm in handling. As such a substrate 1, for
instance, various plastic films or sheets, including polyesters
such as polyethylene terephthalate, polyarylates, polycarbonates,
polyurethanes, polyimides, polyetherimides, cellulose derivatives,
polyethylenes, ethylene-vinyl acetate copolymers, polypropylenes,
polystyrenes, acrylic resins, polyvinyl chlorides, polyvinylidene
chlorides, polyvinyl alcohols, polyvinyl butyrals, nylons,
polyether ether ketones, polysulfones, polyether sulfones,
tetrafluoroethylene-perfluoroalkyl vinyl ethers, polyvinyl
fluorides, tetrafluoroethylene-ethylene,
tetrafluoroethylene-hexafluoropropylene,
polychlorotrifluoroethylenes, polyvinylidene fluorides, and the
like, can be enumerated. Further, the thickness of the substrate 1
can be appropriately set depending on the material to be used so
that the strength and the heat resistance thereof become
appropriate values, and may be in the range of about 2.5 to 100
.mu.m in general, and preferably, in the range of about 1 to 10
.mu.m.
(Heat-Resistant Lubricating Layer)
As shown in FIGS. 1 to 6, the heat-resistant lubricating layer 7
which comprises one or more layers is provided on one surface of
the substrate 1 (the lower surface of the substrate 1 in the case
shown in FIG. 1). In the thermal transfer sheet according to the
present invention, the back face layer 5 is invariably included in
the heat-resistant lubricating layer 7, in either of the case that
the heat-resistant lubricating layer is composed of one layer, and
the case that it is composed of two or more layers. Therefore, when
the heat-resistant lubricating layer 7 is composed of one layer,
the back face layer 5, per se, becomes the heat-resistant
lubricating layer 7, and as a result, the organic minute particles
20 each having the polygonal shape are contained in the back face
layer 5. On the other hand, in the case that the heat-resistant
lubricating layer 7 comprises two or more of the layers, the back
face layer 5 is arranged at a position farthest from the substrate
1 in heat-resistant lubricating layer. Hereinafter, with respect to
the heat-resistant lubricating layer 7, the case where the
polygonal shaped organic minute particles 20 are contained in the
back face layer 5 and a portion of the surfaces of the polygonal
shaped organic minute particles 20 protrudes from the surface of
the back face layer 5, and the case where the polygonal shaped
organic minute particles 20 are contained in the layer (s) other
than the back face layer 5 and a portion of the surfaces of the
polygonal shaped organic minute particles 20 protrudes from the
surface of the back face layer 5, will be described separately.
(Heat-Resistant Lubricating Layer of the First Embodiment)
As shown in FIGS. 1-4, the heat-resistant lubricating layer 7 of
the first embodiment is composed of one, or two or more layers,
including a back face layer 5 as an essential component.
(Back Face Layer in the First Embodiment)
In the heat-resistant lubricating layer 7 of the first embodiment,
the back face layer 5 contains a binder resin and the polygonal
shaped organic minute particles 20, and a portion of the surfaces
of the polygonal shaped organic minute particles 20 which contained
in the back face layer 5 protrudes from the surface of the back
face layer 5. Now, the polygonal shaped organic minute particles
20, and the binder resin will be explained.
"Polygonal Shaped Organic Minute Particles"
As shown in FIGS. 1-4, in the back face layer 5 which constitutes
the heat-resistant lubricating layer, the organic minute particles
20 each having polygonal shape are contained. With respect to the
polygonal shaped organic minute particles 20 located near the
surface of the back face layer 5, a portion of the surface of the
organic minute particles protrudes from the surface of the back
face layer 5. In the present invention, by the polygonal shaped
organic minute particles that protrude from the surface of the back
face layer 5, a scraping performance against the residue attached
to the thermal head is imparted to the heat-resistant lubricating
layer 7 which includes the back face layer 5.
In the present invention, the back face layer 5 which constitutes
the heat-resistant lubricating layer contains the organic minute
particles for imparting the performance scraping the residue
adhered to the thermal head, and it is an essential requirement
that the organic minute particles possess polygonal shape.
Accordingly, the organic minute particles each having no corner or
jag, for example, organic minute particles each having spherical
shape, are excluded from the interested polygonal shaped organic
minute. Herein, the above mention is not intended to prohibit the
spherical shaped organic minute particles from containing in the
back face layer 5 which constitutes the heat-resistant lubricating
layer. As long as the polygonal shaped organic minute particles 20
are contained, any organic minute particles other than this
polygonal shape may be arbitrarily contained therein. Hereinafter,
unless otherwise noted, in the case of being described as "organic
minute particles" simply, it means the polygonal shaped organic
minute particles.
Next, the mechanism for scraping the residue which is derived from
the component of the back face layer and is adhered to the thermal
head, by the polygonal shaped organic minute particles 20 on
running of the thermal head will be explained. As can be seen in
figures, through the surface of the back face layer 5 which
constitutes the heat-resistant lubricating layer, a portion of the
surface of the polygonal shaped organic minute particles 20
protrudes. Thus, certain asperities are given to the surface of the
back face layer 5 constituting the heat-resistant lubricating
layer, by the organic minute particles 20 which thus protrude.
Since the organic minute particles 20 are harder than the resin
contained in the back face layer 5 which constitutes the
heat-resistant lubricating layer, the residue adhered to the
thermal head will be removed as being scraped by convex portions
that are formed on the surface of the back face layer 5 on running
of the thermal head. Furthermore, in the present invention, since
the organic minute particles which contribute to the formation of
the asperities are polygonal shapes, corners are also present on
the protruding portions, i.e. the convex portions, and a very high
scraping effect to the residue will be exhibited by these
corners.
Further, since the interested component contained in the back face
layer 5 which constitutes the heat-resistant lubricating layer is
the organic minute particles 20 as described above, there is no
fear that the component wears down the thermal upon scraping the
residue adhered to the thermal head, in contrast to the case of
using inorganic minute particles. In other words, it is possible to
prevent wear of the thermal head by adopting the organic minute
particles which protrude in a part from the surface of the back
face layer 5 which constitutes the heat-resistant lubricating
layer. As a result, it becomes possible to prevent the occurrence
of printing inferiority, such as printing wrinkle and printing
faint, which may be caused by the wearing of the thermal head, and
further to prevent the printer from becoming shortened its useful
life, which is also accompanied by the wearing of the thermal
head.
There is no particular limitation for the particle diameter of the
polygonal shaped organic minute particles 20 which are contained in
the back face layer 5 which constitutes the heat-resistant
lubricating layer. However, in the case that the particle diameter
of the organic minute particles 20 is markedly small, for example,
it is less than 0.3 .mu.m, there is a possible case that it becomes
difficult to protrude a portion of the organic minute particles
through the surface of the back face layer 5, even if the organic
minute particles has been adequately dispersed in the liquid for
forming the back face layer 5 which constitutes the heat-resistant
lubricating layer. On the other hand, in the case that the particle
diameter of the organic minute particle are increased considerably,
for example, it is greater than 15 .mu.m, there is a possible case
that the organic minute particles 20 are dropped out of the back
face layer 5 on the running of the thermal head.
Considering these points, it is preferable that the particle
diameters of the polygonal shaped organic minute particle 20 to be
contained in the back face layer which constitutes the
heat-resistant lubricating layer is in the range of not less than
0.3 .mu.m and not more than 15 .mu.m, and more particularly, in the
range of not less than 4 .mu.m and not more than 11 .mu.m. In
particular, by setting the particle diameter within the range of
not less than 4 .mu.m and not more than 11 .mu.m, it is possible to
improve the performance of scraping minute sludge adhered to the
thermal head. Furthermore, when the thickness of the back face
layer 5 which constituted the heat-resistant lubricating layer is
appropriately adjusted while the particle diameter is set within
the above mentioned range, it becomes possible to put the volume of
the part of the organic minute particles which protrudes through
the surface of the back face layer to be smaller than the volume of
the remaining part of the organic minute particles which is
embedded in the back face layer, and thus to set the protruding
amount to be less shedding frequency on the running of the thermal
head.
Herein, the particle diameter of the organic minute particles 20 is
an average particle diameter measured by a particle size
distribution measuring apparatus in accordance with the laser
diffraction scattering method, and is a volume average particle
diameter calculated by volume basis. As the particle size
distribution measuring apparatus, for instance, it is possible to
utilize a Coulter LS230, manufactured by Beckman-Coulter, Inc.,
etc. This is similarly applicable to the organic minute particles
20 contained in the heat-resistant lubricating layer of the second
embodiment which will be described below.
By incorporating the above mentioned polygonal shaped organic
minute particles 20 into the back face layer 5 which constitutes
the heat-resistant lubricating layer 7, the thermal transfer sheet
of the present invention can satisfy both of the suppression
performance to the residue adhering to the thermal head, and an
anti-wearing performance to the thermal head. As the polygonal
shaped organic minute particles 20, for instance, silicone resin
particles, fluorine-containing resin filler, particles made of an
organic resin, such as acrylic resin, lauroyl resin, phenol resin,
acetal resin, polystyrene resin, nylon resin, etc., and particles
made of a cross-linked resin in which any of above mentioned resin
was reacted with a cross-linking agent, may be enumerated, but it
is not limited thereto, and may be appropriately selected and used
from organic particles known in the art, as long as the organic
particles to be used meet the requirement of being the polygonal
shape.
Further, it is preferable that the polygonal shaped organic
particles possess a high heat resistance. By incorporating the
polygonal shaped organic minute particles having high heat
resistance into the back face layer 5, it is possible to prevent
that a thermal head and the surface of the back face layer 5 causes
a thermal fusion on printing, and further it becomes possible to
prevent the occurrence of printing flaws due to interference with
traveling of the thermal transfer sheet by such a thermal fusion.
As the organic minute particles having high heat resistance, for
instance, the silicone resin minute particles, etc., can be
enumerated.
As the organic minute particles, it is also possible to use any
commercially available product, as-is, and as the silicone resin
minute particles, for example, Tospearl 120, manufactured by
Momentive Performance Materials Japan LLC and MSP-4000,
manufactured by Nikko Rika Corp., etc., can be enumerated. The
silicone resin minute particles mentioned above (Tospearl 240 has a
thermal decomposition temperature of 420.degree. C., and the
silicone resin minute particles (MSP-4000 has a thermal
decomposition starting temperature of not less than 350.degree.,
and thus they are excellent in the heat resistance, they can be
suitably used in the present invention.
Although there is no particular limitation for the addition amount
of the polygonal shaped organic minute particles 20 to be contained
in the back face layer 5, but when the addition amount of the
organic minute particles 20 is less than 0.01% by weight on the
basis of the solid content of the back face layer 5, there is a
possibility that the degree of protrusions by the organic minute
particles 20 on the surface of the back face layer 5 is reduced,
which will be followed by insufficient performance of scrapping the
residue. On the other hand, when the addition amount of the organic
minute particles 20 is more than 3% by weight, there is a
possibility that friction between the thermal head and the back
face layer 5 is increased, which will be followed by occurrence of
printing wrinkle, or printing defect. Considering these points, it
is preferable that the adding amount of the organic minute
particles 20 is to be in the range of not less than 0.01% by weight
and not more than 3% by weight on the basis of the basis of the
solid content of the back face layer 5.
(Binder Resin)
As the resin to be included in the back face layer 5, there is no
particular limitation, and, for instance, polyvinyl acetal resins,
polyvinyl butyral resins, acrylic resins, polyester resins,
styrene-maleic acid copolymers, polyimide resins, polyamide resins,
polyamide-imide resins, cellulose acetate propionate, cellulose
acetate butyrate, cellulose acetate, polyvinylidene fluoride,
nylons, polyvinyl carbazole, chlorinated rubbers, cyclized rubber
and polyvinyl alcohol, may be enumerated. In consideration of the
heat resistance, those of which have a glass transition point of
not less than 60.degree. C. resins are preferably used.
In addition, it is said that the binder resin contained in the back
face layer 5 gives a significant impact on the cross-linking
density of the back face layer 5. And, in general, as the
cross-linking density of the back face layer 5 becomes high, the
heat resistance of the back face layer 5 is improved more. On the
other hand, in the case that it is allowed to contain a lubricant
component to the backing layer 5, if the cross-linking density of
the back face layer 5 is set too high, it becomes impossible to
bleed sufficiently the lubricant component to the surface of the
back face layer 5 on the running of the thermal head, and thus, it
will become a factor of blocking the action of the lubricant
component.
Accordingly, with respect to the binder resin to be contained in
the back face layer 5, it is preferable that its cross-linking
density is adjusted to a degree at which the action of the
lubricant component is never blocked while imparting a certain heat
resistance to the back face layer 5. Considering these points, it
is preferable that the binder resin contained in the back face
layer 5 is a cured resin in which one or both of a polyvinyl
butyral resin which has many hydroxyl groups (--OH) in its molecule
and a polyvinyl acetal resin such as polyvinyl acetoacetal resin
was cured by an isocyanate curing agent, and a molar equivalent
ratio of hydroxyl groups included in one or both of the polyvinyl
butyral resin and the polyvinyl acetal resin and isocyanate groups
of the isocyanate curing agent, (--NCO/--OH), is not less than 0.01
and less than 0.7.
In the case that this cured resin is applied, since the binder
resin is cured within a defined range, it becomes possible to
impart a heat resistance to the back face layer 5, the level of
which is no problem in use, and possible to bleed the lubricant
component, which is optionally contained in the back face layer, to
the surface of the back face layer 5 on the printing, so that the
lubricant component can be sufficiently exerted its function.
It is preferable that the polyvinyl acetal resin for forming the
cured resin has a hydroxyl value of being not less than 9% by
weight and not more than 25% by weight. When satisfying this range,
it is possible to improve the heat resistance, and to dissolve
readily in a solvent, such as toluene and ethyl acetate. As the
polyvinyl acetal resin having such a degree of the hydroxyl value,
for instance, S-LEC BX-L, BX-1, BX-5, KS-1, KS-3, KS-5, KS-10,
manufactured by Sekisui Chemical Co., Ltd., and the like can be
enumerated. Herein, in this specification, the term "hydroxyl
value" is intended to mean the proportion of monomer component
having hydroxyl group in a resin polymer, and it is calculated as
the ratio of the weight of the monomer component having the
hydroxyl group to the total weight of the resin polymer (% by
weight).
Isocyanate curing agent is one that functions to improve the film
strength or heat resistance of the heat resistant lubricating
layer, by cross-linking the polyvinyl butyral resin, or the
polyvinyl acetal resin as above mentioned with using the hydroxyl
groups of its own. Although a variety of isocyanate curing agents
are conventionally known in the art, it is desirable to use adducts
of aromatic isocyanates. As the aromatic isocyanates, for instance,
2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of
2,4-toluene diisocyanate and 2,6-toluene diisocyanate,
1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene
diisocyanate, trans-cyclohexane, 1,4-diisocyanate, xylylene
diisocyanate, triphenyl methane diisocyanate, tris(isocyanate
phenyl) thiophosphate and the like are enumerated, and, in
particular, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or,
the mixture of 2,4-toluene diisocyanate and 2,6-toluene
diisocyanate is preferred.
"Polyethylene Wax"
The back face layer 5 may contain a polyethylene wax or a talc. The
polyethylene wax is one that functions to improve the slipping
property of the back face layer 5, whereas the above mentioned
polygonal shaped organic minute particles 20 are contained to
satisfy both of the suppression performance to the residue adhering
to the thermal head and the anti-wearing performance to the thermal
head. As the polyethylene wax, polyethylene wax particles having a
density of 0.94 to 0.97, for instance, the particles obtained by
finely powdering the polyethylene wax, are preferred. As the
polyethylene wax, high-density or low-density polyethylene waxes
are available. The low-density polyethylene contains ethylene
polymers that are structurally branched in a large proportion. On
the other hand, the high-density polyethylene is mainly constituted
by linear structures of polyethylene.
As the polyethylene wax, those having a mean particle diameter of
being not less than 1 .mu.m and not more than 15 .mu.m are suitable
to be used. When the polyethylene wax having the mean particle
diameter within the above defined range is contained, it is
possible that a portion of the high-density polyethylene wax is
protruded through the surface of the back face layer 5 to improve
the slipping property of the thermal transfer sheet. Further, in
combination with the scraping effect to the residue adhering to the
thermal head which is owing to the polygonal shaped organic minute
particle as described above, it is possible to further improve the
performance of scraping the residue adhering to the thermal
head.
Preferably, the polyethylene wax is contained at a ratio of 1% to
15% by weight on the basis of the total solid content of the back
face layer. When the content is set within the above defined range,
it is possible to impart a particularly excellent slipping property
to the back face layer 5. Preferably, the polyethylene wax has a
melting point of 110 to 140.degree. C.
"Talc"
From the same viewpoint as the polyethylene wax, it is preferable
that the talc is contained in the back face layer 5, instead of the
polyethylene wax, or in company with the polyethylene wax.
As the talc, the one which has a particle diameter of not less than
1 .mu.m and not more than 15 .mu.m is preferably used. Effects due
to inclusion of the talc of this range are the same as those of the
polyethylene wax described above.
It is preferable that the talc is contained in a ratio of 1% by
weight and not more than 10% by weight on the basis of the total
solid content of the back face layer. By using the above range in
content, it is possible to impart a particularly excellent
lubricity to the back face layer 5. Note that, when the talc is
used in conjunction with the polyethylene wax, it is preferable
that the total weight of the talc and the polyethylene wax is
within the above range.
Further, it is also possible to add a metallic soap, phosphoric
acid ester, etc., as a lubricant, to the back face layer 5. As the
metallic soap, for example, multivalent metallic salts of alkyl
phosphoric esters, metallic salts of alkyl carboxylic acid, etc.,
may be enumerated. As the above mentioned multivalent metallic
salts of alkyl phosphoric esters, the ones which are known in the
art as additive for plastics may be used. The above mentioned
multivalent metallic salt of alkyl phosphoric ester can be
obtained, in general, by substituting an alkali metallic salt of
the alkyl phosphoric ester with a polyvalent metal, and the ones of
various grades may be available.
As the phosphoric acid ester, for example, (1 phosphoric monoesters
or diesters of saturated or unsaturated higher alcohols having a
carbon number of 6 to 20, (2 phosphoric monoesters or diesters of
polyoxyalkylene alkyl ethers or polyoxyalkylene alkyl allyl ethers,
(3 phosphoric diesters or monoesters of alkylene oxide adducts
(average addition molar number: 1-8 of the above mentioned
saturated or unsaturated alcohols, (4 phosphoric monoesters or
diesters of alkyl phenols or alkyl naphthols which have an alkyl
group having a carbon number of 8-12, are enumerated. As the
saturated and unsaturated higher alcohols for the above (1 and (3
compounds, for example, cetyl alcohol, stearyl alcohol, oleyl
alcohol, etc., are enumerated. As the alkyl phenol for the above (3
compounds, for example, nonyl phenol, dodecyl phenol, diphenyl
phenol, etc., are enumerated.
"Other ingredients"
Further, in the back face layer 5, in order to adjust the slipping
of back face layer ancillary, it is possible to add inorganic
minute particles or a silicone oil. As the inorganic minute
particles, for example, clay minerals such as kaolin, carbonates
such as calcium carbonate, magnesium carbonate, and hydroxides such
as aluminum hydroxide, magnesium hydroxide, sulfate salts such as
calcium sulfate, oxides such as silica, inorganic minute particles
such as graphite, niter, boron nitride, and the like are
enumerated.
As the inorganic minute particles described above, those of having
an average particle diameter of about 0.3 .mu.m-3 .mu.m is
preferably used. Further, it is preferable that the inorganic
minute particles described above is used in a ratio of not less
than 5 part by weight and not more than 40 part by weight, when the
total weight of both of or ether of the polyvinyl acetal resin and
the polyvinyl butyral resin used is taken as 100 parts by weight.
By adopting this range, it is possible to improve the lubricity and
to improve the film flexibility and the film strength of the back
face layer.
There is no particular limitation for the thickness of the back
face layer 5 which constitutes the heat-resistant lubricating layer
7, as long as the thickness can be made to protrude a portion of
the surface of the polygonal shaped organic minute particles 20
through the surface of the back face layer 5. Herein, a possibility
that organic minute particles 20 fall out of the back face layer 5
is increased, if the thickness of the back face layer 5 is too thin
in comparison with the particle diameter of the polygonal shaped
organic minute particles 20. On the other hand, a possibility that
no portion of the surface of the organic minute particles protrude
through the surface of the back face layer 5 is increased, if the
thickness of the back face layer 5 is too thick in comparison with
the particle diameter of the polygonal shaped organic minute
particles 20.
There is no particular limitation about the method for forming the
back face layer 5 which constitutes the heat resistant lubricating
layer 7 of the first embodiment. The back face layer 5 may be
formed by dissolving or dispersing the above mentioned the binder
resin, and the polygonal shaped organic minute particles as the
essential ingredients, and optionally, other various ingredients to
be added, into a suitable solvent in order to prepare a coating
liquid for forming the back face layer; coating thus prepared
coating liquid onto the substrate 1 or onto any other layer which
constitutes the heat resistant lubricating layer 7, in accordance
with a known coating procedure such as the gravure printing method,
the reverse roll coating method using a gravure plate, the roll
coater, the bar coater or the like; and then drying the coated
liquid.
Incidentally, the heat-resistant lubricating layer 7 of the first
embodiment, may be composed only of the back face layer 5 which
contains the polygonal shaped organic particles, as shown in FIGS.
1 and 2. Alternatively, it may be composed of two or more layers
which include the back face layer 5 which contains the polygonal
shaped organic particles and other layer (s), as shown in FIGS. 3
and 4. Even in either configuration, by the presence of the
polygonal shaped organic minute particles, a portion of the surface
of the particles protruding through the surface of the back face
layer 5, it is possible to prevent wearing of the thermal head as
described above. As the other optional layer(s), for instance, a
primer layer 6 as shown in the figures, an antistatic layer, etc.,
can be enumerated. The other optional layer(s) may be one, or two
or more.
(Primer Layer)
As shown in FIGS. 3, 4, it is possible to provide the primer layer
6 between the back face layer 5 and the substrate 1, a layer of any
other constituting the heat-resistant lubricating layer 7, as the
other optional layer(s) which constitutes the heat-resistant
lubricating layer 7. The primer layer 6 constituting the
heat-resistant lubricating layer 7 is a layer which is provided in
order to improve the adhesion between the substrate 1 and the back
face layer 5 constituting the heat-resistant lubricating layer 7.
As the binder resin contained in the primer layer 6, for example,
polyester resins, polyurethane resins, acrylic resins,
polycarbonate resins, polyvinyl alcohol resins, vinyl
chloride-vinyl acetate copolymer, polyvinyl butyral resins, etc.,
may be enumerated.
Further, the primer layer 6 may contain a curing agent, an adhesion
promoter, an antistatic agent. As the adhesion promoter, aqueous
polyurethanes, aqueous polyesters, water-based acrylic resins,
etc., may be enumerated. Among them, the one which has a glass
transition temperature (Tg) of more than 50.degree. C. is
preferable. As the antistatic agent, for example, fine metal oxide
powder of tin oxide or the like, conductive materials having a
.pi.-electron conjugated structure such as sulfonated polyaniline,
polythiophene, polypyrrole or the like may be enumerated.
There is no particular limitation about the method of forming the
primer layer 6. The primer layer 6 may be formed, for instance, by
dissolving or dispersing the above mentioned the binder resin, and
optionally, other ingredients to be added, such as the curing
agent, the adhesion promoter, the antistatic agent, etc., into a
suitable solvent in order to prepare a coating liquid for forming
the primer layer; coating thus prepared coating liquid onto the
substrate 1, in accordance with a known coating procedure such as
the gravure printing method, the reverse roll coating method using
a gravure plate, the roll coater, the bar coater or the like; and
then drying the coated liquid.
Although there is no particular limitation about the thickness of
the primer layer 6, but it is preferable to be in the range of
about 0.01 .mu.m-0.3 .mu.m, in consideration of heat resistance and
adhesiveness.
Further, it is possible to provide another layer between the back
face layer 5 and the substrate 1, in conjunction with or instead
of, the primer layer 6 As another layer, for example, an antistatic
layer or the like may be enumerated.
(Heat-Resistant Lubricating Layer of the Second Embodiment)
As shown in FIGS. 5 and 6, the heat-resistant lubricating layer 7
of the second embodiment is composed of two or more layers which
include a backing layer 5. In this embodiment, among the layers
constituting the heat-resistant lubricating layer 7, the polygonal
shaped organic minute particles 20 are contained in the layer other
than the back face layer 5. And, a configuration that a portion of
the surfaces of the polygonal shaped organic minute particles 20
which are contained in the layer other than the back face layer 5
protrude through the surface of the back face layer 5 is taken in
this embodiment. Hereinafter, the layer into which the polygonal
shaped organic minute particles are contained and which is other
than the back face layer 5 will be sometimes referred to as "other
layer".
The thermal transfer sheet of the second embodiment, the polygonal
shaped minute particles 20 are contained in the "other layer" other
than the back face layer 5. Accordingly, in the this embodiment,
the heat-resistant lubricating layer 7 include two or more layers
which comprise the back face layer 5 and the "other layer(s)". The
back face layer 5 is arranged at a position farthest from the
substrate 1 among the layers constituting the heat-resistant
lubricating layer 7.
The heat-resistant lubricating layer 7 of the second embodiment is
different from the heat-resistant lubricating layer of the first
embodiment described above in that the layers to contain the
polygonal shaped minute particles 20 are different mutually. In
other words, the heat-resistant lubricating layer 7 of the second
embodiment is different from the heat-resistant lubricating layer
of the first embodiment described above in that the polygonal
shaped organic minute particles are contained in the "other layer"
and a portion of the surfaces of the polygonal shaped organic
minute particles 20 which are contained in the "other layer"
protrude through the surface of the back face layer 5, in the
second embodiment.
However, the point that a portion of the surfaces of the polygonal
shaped organic minute particles 20 protrude through the surface of
the back face layer 5, per se, is common in the heat-resistant
lubricating layer of the first embodiment and the heat-resistant
lubricating layer of the second embodiment. Owing to this
community, the heat-resistant lubricating layer 7 of the second
embodiment can enjoy the same functions and effects as the
heat-resistant lubricating layer of the first embodiment described
above.
(Other Layer)
There is no particular limitation about the "other layers" into
which the polygonal shaped organic minute particles are contained,
and it is possible to employ any layer provided between the back
face layer 5 and the substrate 1. For example, as shown in FIGS. 5
and 6, the primer layer 6 for improving the adhesiveness between
the back face layer 5 and the substrate 1 may be adopted as the
"other layer". Alternatively, yet another layer may be adopted as
the "other layer". As the "other layer" other than the primer layer
6, for example, an antistatic layer or the like can be enumerated.
In the thermal transfer sheet 10 of the embodiment illustrated in
these figures, the primer layer 6 is provided as "other layer"
between the substrate 1 and the back face layer 5, and in this
primer layer 6, the polygonal shaped organic minute particles 20
are contained. Further, a portion of the surface of the polygonal
shaped organic minute particles 20 contained in the primer layer 6
is protruded through the surface of the back face layer 5. Now, the
"other layer" will be described by taking the primer layer 6 as a
typical example. However, it should be noted that the primer layer
6, per se, is an optional constituent in the thermal transfer sheet
10 according to the present invention, and the thermal transfer
sheet 10 of this embodiment.
Instead of the thermal transfer sheet 10 of the embodiment shown in
FIGS. 5 and 6, it is possible to provide "other layer (s)", which
will bring one or more of various functions, between the primer
layer 6 and the back face layer 5, and to allow the "other layer"
provided between the primer layer 6 and the back face layer 5 to
contain the polygonal shaped organic minute particles 20. In
addition, it is also possible to provide "other layer(s)", which
will bring one or more of various functions, between the substrate
1 and the primer layer 6, and to allow the "other layer" provided
between the substrate 1 and the primer layer 6 to contain the
polygonal shaped organic minute particles 20.
In the "other layer", a binder resin and the polygonal shaped
organic minute particles 20 are contained. with respect to the
polygonal shaped organic minute particles 20 in this embodiment,
unless otherwise specified, those described in the thermal transfer
sheet 10 of the first embodiment can be appropriately selected and
used, and thus, the description thereof is omitted here.
Although there is no particular limitation for the particle
diameter of the organic minute particles 20 to be contained in the
"other layers", but organic minute particles 20 having a particle
diameter of at least greater than the thickness of the back face
layer 5 is contained in the "other layer". In the case that the
particle diameter of the organic minute particles 20 contained in
the "other layer" is less than the thickness of the back face layer
5, it is impossible that a portion of the surface of the organic
minute particles 20 protrudes through the surface of the layer 5 as
shown in FIGS. 5 and 6.
Therefore, it is necessary to select an optimal particle diameter
of the organic minute particle 20 in consideration of the thickness
of the back face layer and the thickness of the "other layer".
Further, when further other distinct layer(s) is provided between
the "other layer" and the back face layer 5, it is necessary to
select an optimal particle diameter of the organic minute particle
20 in consideration of the thickness of the further other distinct
layer(s) as well as the thickness of the back face layer and the
thickness of the "other layer".
In the "other layer", a binder resin for holding the organic
particles 20 is included. There is no particular limitation about
the binder resin, and it may be appropriately selected depending on
the functionality of such a "other layer". For instance, it is
possible to use any of the binder resins as described in the back
face layer 5 of the first embodiment and the binder resins
described in the primer layer 6, upon an appropriate selection. It
is also possible to use a binder resin other than those. The binder
resin contained in the "other layer", may be one single kind, or
may be used in combination of two or more kinds thereof.
There is no particular limitation for the addition amount of the
polygonal shaped organic minute particles 20 to be contained in the
"other layer", as long as the amount is within the range of not
degrading the functions or the like which are required to the back
face layer 5. For instance, when the organic minute particles 20 is
added to the primer layer 6, it is preferable that the addition
amount of the organic minute particles 20 is not less than 0.01% by
weight and more than 3% by weight, on the basis of the total solid
content of the primer layer 6. Further, in the case that the
organic minute particles 20 are added to the primer layer 6, there
is no especially limitation about the particle diameter of the
organic minute particles 20, and the particle diameter may be
decided within the range that allows a portion of the surface of
the organic minute particles to protrude through the surface of the
heat-resistant lubricating layer 7, in consideration of the
thickness of the primer layer 6 and the thickness of the back face
layer 5.
The back face layer 5 of the second embodiment and the back face
layer 5 in the first embodiment differs only in terms of whether or
not containing the polygonal shaped organic minute particles 20,
but are just the same about the other points as described in the
back face layer 5 of the first embodiment. Therefore, as the back
face layer 5 contained in the heat-resistant lubricating layer 7 of
the thermal transfer sheet 10 according to the second embodiment,
it is possible to use a construction of the back face layer 5
described in the thermal transfer sheet according to the first
embodiment, excluding the polygonal shaped organic minute particles
20.
It is preferable that the binder resin contained in the back face
layer 5 of the second embodiment is a cured resin in which one or
both of polyvinyl butyral resin and polyvinyl acetal resin was
cured by an isocyanate curing agent. When such a cured resin is
included in the back face layer 5 of the second embodiment, it
becomes possible to hold firmly the organic minute particles 20
which protrude through the surface of the "other layer" by the
cured resin which is included in the back face layer 5, and to
prevent effectively the detachment of the organic minute particles
20.
With respect to the heat-resistant lubricating layer which
constitutes the thermal transfer sheet 10 according to the present
invention, those of the first embodiment and the second embodiment
are described in detail as above. However, without deviating from
the scope and the spirit of the present invention, various changes
and modifications may be applied to these embodiments. For example,
in the case where the heat-resistant lubricating layer 7 is
composed of two or more layers which includes a backing layer 5, it
is possible to adopt any of configurations where the heat-resistant
lubricating layer of the first embodiment and the heat-resistant
lubricating layer of the second embodiment are used in combination,
concretely, a configuration where both the back face layer 5 and
the "other layer" contain the polygonal shaped organic minute
particles, and each individual portions of the surfaces of the
organic particles 20 contained in the respective layers protrude
through the back face layer 5.
The invention is characterized in that the back face layer 5 as
described above on one surface of the substrate 1 is provided.
Therefore, there is not particular limitation about layer(s) which
is provided on the other surface of the substrate 1. For example,
it is possible to provide a transcriptive protective layer or a
color material layer which are known in the field of thermal
transfer sheet.
(Transcriptive Protective Layer)
In the embodiment shown in FIGS. 1, 3, 5, the transcriptive
protective layer 3 which is capable of exfoliating from the
substrate 1 is formed on another surface of the substrate 1 which
is opposite to the surface of the substrate 1 on which the back
face layer is formed (upper surface of the substrate 1 in the cases
shown in FIGS. 1, 3, 5). The transcriptive protective layer 3 is
provided in order to impart gloss to the printed matter to which
the transcription protective layer 3 is transferred, while
improving the durability of the printed matter. Herein, the
transcriptive protective layer 3 is an optional configuration in
the thermal transfer sheet according to the present invention.
Material for forming the transcriptive protective layer 3 is not
particularly limited as long as the material has transparency and
glossiness. As such a material, for example, methacrylic acid ester
copolymers, vinyl chloride-vinyl acetate copolymers, polyester
resins, polycarbonate resins, acrylic resins, ultraviolet-absorbing
resins, epoxy resins, polystyrene resins, polyurethane resins,
acrylic urethane resin, silicone modified derivatives of above
mentioned resins, blends of any combination of above mentioned
resins, ionizing radiation-curable resins, ultraviolet-absorbing
resins, etc., are exemplified.
Further, the transcriptive protective layer 3 containing an
ionizing radiation curable resin may be suitably used as a material
of the transcriptive protective layer 3 in that the plasticizer
resistance and the abrasion resistance are particularly excellent.
It is not particularly limited as ionizing radiation curable resin,
and can be suitably selected from conventionally known ionizing
radiation curable resins, for example, a resin formed by
cross-linking and curing a radically polymerizable polymer or
oligomer through ionizing radiation irradiation and, optionally,
adding a photopolymerization initiator thereto, and then performing
polymerization cross-linking by applying an electron beam or
ultraviolet light may be used. The transcriptive protective layer 3
containing an ultraviolet-absorbing resin is excellent in giving a
light resistance to the printed matter.
As the ultraviolet absorbing resin, for example, it is possible to
react to the ionizing radiation curable resin of the thermoplastic
resin or a reactive UV absorber and a resin obtained by bonded.
Specifically, the organic UV absorbers salicylate, benzophenone,
benzotriazole, substituted acrylonitrile, nickel chelate-based,
non-reactive known as hindered amine-based, dual addition
polymerizable more I include those introduced (vinyl group, for
example, acryloyl group, methacryloyl group, etc.) binding,
alcoholic hydroxyl group, an amino group, a carboxyl group, an
epoxy group, a reactive group such as an isocyanate group.
There is no particular limitation about the thickness of the
transcriptive protective layer 3. When the thickness of the
transcriptive protective layer 3 is thinner than 0.1 .mu.m,
however, it may be difficult to give durability on the surface of
the printed matter onto which the transcriptive protective layer 3
was transferred. Considering these points, the thickness of the
transcriptive protective layer 3 is usually in the range of about
0.1-10 .mu.m, and preferably, about 0.5-5.0 .mu.m.
Further, in the transcriptive protective layer 3, a agent for
improving the sliding properties to the article for receiving
transcription, such as silicon filler, talc, kaolin, mica,
graphite, calcium carbonate, molybdenum disulfide, silicone rubber
filler, benzoguanamine resins, melamine-formaldehyde condensates or
the like may be contained.
The method of forming the transcriptive protective layer 3, with an
appropriate solvent to prepare a transcriptive protective layer
coating solution by dispersing or dissolving one or more of the
resin to the substrate 1 on this It can be applied by conventional
means known reverse coating method or the like using a gravure
printing method, a gravure plate or a screen printing method to
form by drying.
(Color Material Layer)
In the embodiment shown in FIGS. 2, 4, 6, a color material layer 4
is formed on another surface of the substrate 1 which is opposite
to the surface of the substrate 1 on which the back face layer is
formed (upper surface of the substrate 1 in the cases shown in
FIGS. 2, 4, 6).
When the thermal transfer sheet according to the present invention
is a sublimation type thermal transfer sheet, sublimable
dye-containing color material layers are formed as the color
material layer. On the other hand, when the thermal transfer sheet
according to the present invention is a heat-fusion type thermal
transfer sheet, the color material layer comprises a heat-fusion
composition which contains coloring agent, and becomes a color
material layer containing heat-fusion ink. In addition, for
instance, a color material layer containing a sublimable dye and
another color material layer containing a heat-fusion type ink
which comprises a heat-fusion type composition with a dye, may be
provided on one continuous substrate as being frame sequentially.
The thermal transfer sheet according to the present invention will
be described by taking a sublimation type thermal transfer sheet as
a typical example. However, it should be noted that the thermal
transfer sheet according to the present invention is not limited to
the sublimation type thermal transfer sheet only.
As the materials for the color material layer 4, any conventionally
known dyes may be used. Among them, the ones which have good
characteristics for the printing material, for instance, the ones
which possess an adequate coloring density, and which can be hardly
discolored or faded by light, heat, or temperature are preferable.
Examples of such dyes include diarylmethane dyes; triarylmethane
dyes; thiazole dyes; merocyanine dyes; pyrazolone dyes; methine
dyes; indoaniline dyes; azomethine dyes such as acetophenone
azomethine dyes, pyrazolo azomethine dyes, imidazol eazomethine
dyes, imidazo azomethine dyes, and pyridone azomethine dyes;
xanthene dyes; oxazine dyes; cyanostyrene dyes such as
dicyanostyrene dyes and tricyanostyrene dyes; thiazine dyes; azine
dyes; acridine dyes; benzeneazo dyes; azo dyes such as, pyridoneazo
dyes, thiopheneazo dyes, isothiazoleazo dyes, pyrroleazo dyes,
pyrazoleazo dyes, imidazoleazo dyes, thiadiazoleazo dyes,
triazoleazo dyes, and disazo dyes; spiropyran dyes;
indolinospiropyran dyes; fluoran dyes; rhodaminelactam dyes;
naphthoquinone dyes; anthraquinone dyes; and quinophthalone dyes.
Concretely, red dyes such as MSRedG (manufactured by Mitsui Toatsu
Chemicals, Inc.), Macrolex Red Violet R (manufactured by Bayer),
CeresRed 7B (manufactured by Bayer), Samaron Red F3BS (manufactured
by Mitsubishi Chemical Co., Ltd.); yellow dyes such as Holon
brilliant yellow 6GL (manufactured by Clariant), PTY-52
(manufactured by Mitsubishi Chemical Industries, Ltd.), MACROLEX
Yellow 6G (manufactured by Bayer); blue dyes such as Kayaset Blue
714 (manufactured by Nippon Kayaku Co., Ltd.), Waxoline Blue AP-FW
(manufactured by ICI), Holon Brilliant Blue S--R (manufactured by
Sandoz), MS Blue 100 (manufactured by Mitsui Toatsu Chemical Co.,
Ltd.), C. I. Solvent Blue 22; etc., are exemplified.
As the binder resin for supporting such a dye, for instance,
cellulosic resins such as ethylcellulose, hydroxyethylcellulose,
ethylhydroxycellose, hydroxypropylcellulose, methylcellulose,
cellulose acetate, and cellulose tributyrate; vinyl resins such as
polyvinylalcohol, polyvinyl acetate, polyvinylbutyral,
polyvinylacetoacetal, and polyvinylpyrrolidone; acrylic resins such
as poly(meth)acrylate and poly(meta)acrylamide; polyurethane
resins, polyamide resins, polyester resins, and the like. Among
them, cellulosic, vinyl, acrylic, urethane, and polyester resins
are preferable from the points of heat resistance and dye-transfer
efficiency.
The color material layer 4 may be formed by dissolving or
dispersing the dye and the binder resin together with optional
additives such as the releasing agent and fillers, etc., in a
suitable solvent such as toluene, methyl ethyl ketone, ethanol,
isopropyl alcohol, cyclohexane, dimethyl formamide, etc., to
prepare a coating liquid; coating the coating liquid on the
substrate by a conventional method such as gravure printing,
reverse roll coating using a gravure plate, roll coater,
bar-coater, etc.; and drying the coated liquid.
(Releasing Layer)
It is also possible to form a releasing layer 2 between the
transcriptive protective layer 3 and the substrate 1 as shown in
FIGS. 1,3,5. Incidentally, the releasing layer is an optional layer
in the thermal transfer sheet 10 of the present invention. The
resin for forming the releasing layer 2 is not particularly limited
as long as it is known as the releasing resin, for example, waxes,
silicone waxes, silicone resins, silicone-modified resins,
fluorine-containing resins, fluorine-modified resins, polyvinyl
alcohols, acrylic resins, thermally cross-linkable epoxy-amino
resins, thermally cross-linkable alkyd-amino resins, etc., are
enumerated. Further, the releasing layer 2 may be made of one type
resin, or two or more resins. Further, the releasing layer 2 may be
formed by using a catalytic cross-linking agent such as isocyanate
compound, tin-based catalysts, aluminum-based catalyst, etc., in
addition to the releasing resin. Herein, it should be noted, the
releasing layer 2 may be transferred to the transcription receiving
side on transcription, or otherwise, may be remained on the
substrate 1 side. The thickness of the releasing layer 2 is about
0.5-5 .mu.m in general. The releasing layer 2 may be formed, for
instance, by dissolving or dispersing the above mentioned resin to
prepare a coating liquid for forming releasing layer; coating thus
prepared coating liquid onto the substrate in accordance with a
known coating procedure such as the gravure printing method, the
screen printing method, the reverse roll coating method using a
gravure plate, or the like; and then drying the coated liquid.
(Heat Seal Layer)
It is possible to form a heat seal layer (not shown) on the
transcriptive protective layer 3. The heat seal layer is an
optional layer in the thermal transfer sheet 10 of the present
invention and is provided for improving the adhesiveness of the
transcriptive protective layer 3 to an article for receiving
transcription. There is no particular limitation about the material
for forming a heat seal layer, and it is possible to use any of
heat-sensitive adhesives known in the art. It is more preferable
that the heat seal layer is formed with a thermoplastic resin of
which glass transition temperature is in the range of
50-100.degree. C., for example, one which has a refractive index
within the range of 1.52 to 1.59, and has an appropriate glass
transition temperature, and selected from resins having a good
thermal adhesiveness, such as acrylic resins, vinyl chloride-vinyl
acetate copolymer resins, epoxy resins, polyester resins,
polycarbonate resins, butyral resins, polyamide resins, vinyl
chloride resin, etc.
There is no particular limitation about the method for forming the
heat seal layer. The heat seal layer may be formed by dissolving or
dispersing the above mentioned resin into a suitable solvent, such
as methyl ethyl ketone, toluene, isopropyl alcohol, etc., and
optionally, adding ultraviolet absorber, antioxidant, fluorescent
brightener, inorganic or organic filler component, surfactant,
release agents, etc., to prepare a coating liquid; coating thus
prepared coating liquid in accordance with a known coating
procedure such as the gravure printing method, the reverse roll
coating method using a gravure plate, or the like so as to form;
and then drying the coated liquid so as to form a film of 0.5-10
.mu.m in thickness.
It is also possible to provide the above-mentioned transcriptive
protective layer 3 and the color material layer 4 on the substrate
1 as being frame sequentially.
(Article for Receiving Transcription)
As article for receiving transcription (thermal transfer
image-receiving sheet), which may be used for the transcription of
the thermal transfer sheet 10, any materials known in this art,
such as plain paper, high quality paper, tracing paper, plastic
film, etc., are enumerated and the material to be used is not
particularly limited.
EXAMPLES
Hereinafter, the present invention will be described with referring
to Examples and Comparative Examples. Herein, the simplified
expressions of "part (s)" in this specification mean "part (s) by
weight", unless otherwise especially mentioned.
Example 1
As a substrate, polyethylene terephthalate film which had 6 .mu.m
in thickness was used. On one surface of this substrate, a liquid
for forming releasing layer having the following composition was
coated in accordance with the gravure coating method so as to
obtain a releasing layer having a thickness of 1.0 .mu.m. Then, a
liquid for forming transcriptive protective layer having the
following composition was coated on the releasing layer in
accordance with the gravure coating method so as to obtain a
transcriptive protective layer having a thickness of 1.0 .mu.m. On
other surface of the substrate, a liquid for forming primer layer 1
having the following composition was coated in accordance with the
gravure coating method so as to obtain a primer layer having a
thickness of 0.2 .mu.m. Then, a liquid for forming back face layer
1 having the following composition was coated on the primer layer
in accordance with the gravure coating method so as to obtain a
back face layer having a thickness of 0.5 .mu.m. Thus, the thermal
transfer sheet of Example 1 was prepared.
<Liquid for Forming Releasing Layer>
TABLE-US-00001 Silicone modified acrylic resin 16 parts (Cell top
226, manufactured by DAICEL Corp.) Silicone modified acrylic resin
8 parts (Cell top 227, manufactured by DAICEL Corp.) Vinyl chloride
- vinyl acetate copolymer 2.4 parts (SOLBIN A, manufactured by
Nissin Chemical Industry Co., Ltd,) Curing catalyst 4.5 parts (Cell
top CAT-A, manufactured by DAICEL Corp.) Ultraviolet ray absorber
0.05 parts (Uvitex OB, manufactured by Nippon Ciba-Geigy Corp.)
Toluene 9.8 parts Methyl ethyl ketone 9.8 parts
<Liquid for Forming Transcriptive Protective Layer>
TABLE-US-00002 Vinyl chloride - vinyl acetate copolymer 4.5 parts
(SOLBIN CNL, manufactured by Nissin Chemical Industry Co., Ltd,)
Ultraviolet ray absorber 15 parts (ST-I UVA 40KT, manufactured by
DAICEL Corp.) Acryl resin liquid 15 parts (LP-45M, manufactured by
Showa Ink Manufacturing Co., Ltd., solid content: 13%)
<Liquid for Forming Primer Layer 1>
TABLE-US-00003 Polyester (solid content: 30%) 16.67 parts (Product
name: POLYESTER WR-961, manufactured by Nippon Synthetic Chemical
Industry Co., Ltd.) Water 41.67 parts Isopropyl Alcohol 41.67
parts
<Liquid for Forming Back Face Layer 1>
TABLE-US-00004 Molar equivalent ratio (--NCO/--OH): 0.53 Polyvinyl
acetal resin 51.2 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 17.8 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
3 .mu.m, 1 part polygonal shape) (MSP-4000, manufactured by Nikko
Rika Corp.) Zinc stearyl Phosphate 10 parts (LBT-1830 purified,
manufactured by Sakai Chemical Industry Co., Ltd.) Zinc stearate 10
parts (SZ-PF, manufactured by Sakai Chemical Industry Co., Ltd.)
Polyethylene wax 10 parts (POLYWAX 3000, manufactured by Toyo ADL
Corp.) methyl ethyl ketone 200 parts toluene 100 parts
Example 2
A thermal transfer sheet of Example 2 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 2 having the following composition.
<Liquid for Forming Back Face Layer 2>
TABLE-US-00005 Molar equivalent ratio (--NCO/--OH): 0.53 Polyvinyl
acetal resin 51.2 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 17.8 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
4 .mu.m, 1 part polygonal shape) (Tospearl 240, manufactured by
Momentive Performance Materials Japan LLC) Zinc stearyl Phosphate
10 parts (LBT-1830 purified, manufactured by Sakai Chemical
Industry Co., Ltd.) Zinc stearate 10 parts (SZ-PF, manufactured by
Sakai Chemical Industry Co., Ltd.) Polyethylene wax 10 parts
(POLYWAX 3000, manufactured by Toyo ADL Corp.) methyl ethyl ketone
200 parts toluene 100 parts
Example 3
A thermal transfer sheet of Example 3 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 3 having the following composition.
<Liquid for Forming Back Face Layer 3>
TABLE-US-00006 Molar equivalent ratio (--NCO/--OH): 0.52 Polyvinyl
acetal resin 47.5 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 16.5 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
4 .mu.m, 1 part polygonal shape) (Tospearl 240, manufactured by
Momentive Performance Materials Japan LLC) Zinc stearyl Phosphate
10 parts (LBT-1830 purified, manufactured by Sakai Chemical
Industry Co., Ltd.) Zinc stearate 10 parts (SZ-PF, manufactured by
Sakai Chemical Industry Co., Ltd.) Polyethylene wax 10 parts
(POLYWAX 3000, manufactured by Toyo ADL Corp.) methyl ethyl ketone
200 parts toluene 100 parts
Example 4
A thermal transfer sheet of Example 4 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 4 having the following composition.
<Liquid for Forming Back Face Layer 4>
TABLE-US-00007 Molar equivalent ratio (--NCO/--OH): 0.21 Polyvinyl
acetal resin 60.6 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 8.4 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
4 .mu.m, 1 part polygonal shape) (Tospearl 240, manufactured by
Momentive Performance Materials Japan LLC) Zinc stearyl Phosphate
10 parts (LBT-1830 purified, manufactured by Sakai Chemical
Industry Co., Ltd. ) Zinc stearate 10 parts (SZ-PF, manufactured by
Sakai Chemical Industry Co., Ltd.) Polyethylene wax 10 parts
(POLYWAX 3000, manufactured by Toyo ADL Corp.) methyl ethyl ketone
200 parts toluene 100 parts
Example 5
A thermal transfer sheet of Example 4 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 5 having the following composition, and the liquid for
forming primer layer 1 was replaced by a liquid for forming primer
layer 2 having the following composition.
<Liquid for Forming Back Face Layer 5>
TABLE-US-00008 Molar equivalent ratio (--NCO/--OH): 0.21 Polyvinyl
acetal resin 60.6 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 8.4 parts (BURNOCK D750,
manufactured by DIC Corporation) Zinc stearyl Phosphate 10 parts
(LBT-1830 purified, manufactured by Sakai Chemical Industry Co.,
Ltd.) Zinc stearate 10 parts (SZ-PF, manufactured by Sakai Chemical
Industry Co., Ltd.) Polyethylene wax 10 parts (POLYWAX 3000,
manufactured by Toyo ADL Corp.) methyl ethyl ketone 200 parts
toluene 100 parts
<Liquid for Forming Primer Layer 2>
TABLE-US-00009 Polyvinyl alcohol resin 2.67 parts (Kuraray POVAL
PVA-117 manufactured by Kuraray Co., Ltd., solid content: 100%,
polymerization degree: 1700) Titanium Chelating agent (solid
content: 42%) 55.5 parts (ORGATIX TC-300, manufactured by Matsumoto
Fine Chemical Co., Ltd. Silicone resin (particle diameter: 4 .mu.m,
0.26 part polygonal shape) (Tospearl 240, manufactured by Momentive
Performance Materials Japan LLC) Water 45.89 parts Isopropyl
Alcohol 45.89 parts
Example 6
A thermal transfer sheet of Example 5 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by the liquid for forming back face
layer 5 having above-mentioned composition, and the liquid for
forming primer layer 1 was replaced by a liquid for forming primer
layer 3 having the following composition.
<Liquid for Forming Primer Layer 3>
TABLE-US-00010 Polyester 16.67 parts (POLYESTER WR-961,
manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid
content: 30%)) Silicone resin (particle diameter: 4 .mu.m, 0.05
part polygonal shape) (Tospearl 240, manufactured by Momentive
Performance Materials Japan LLC) Water 41.67 parts Isopropyl
Alcohol 41.66 parts
Example 7
A thermal transfer sheet of Example 7 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 7 having the following composition.
<Liquid for Forming Back Face Layer 7>
TABLE-US-00011 Molar equivalent ratio (--NCO/--OH): 0.01 Polyvinyl
acetal resin 68.6 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 0.5 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
4 .mu.m, 1 part polygonal shape) (Tospearl 240, manufactured by
Momentive Performance Materials Japan LLC) Zinc stearyl Phosphate
10 parts (LBT-1830 purified, manufactured by Sakai Chemical
Industry Co., Ltd.) Zinc stearate 10 parts (SZ-PF, manufactured by
Sakai Chemical Industry Co., Ltd.) Polyethylene wax 10 parts
(POLYWAX 3000, manufactured by Toyo ADL Corp.) methyl ethyl ketone
200 parts toluene 100 parts
Example 8
A thermal transfer sheet of Example 8 was obtained by carrying out
the same procedure in Example 1 except that the liquid for forming
back face layer 1 was replaced by a liquid for forming back face
layer 8 having the following composition.
<Liquid for Forming Back Face Layer 8>
TABLE-US-00012 Molar equivalent ratio (--NCO/--OH): 0.2 Polyvinyl
acetal resin 60.6 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 8.4 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (particle diameter:
4 .mu.m, 0.01 part polygonal shape) (Tospearl 240, manufactured by
Momentive Performance Materials Japan LLC) Zinc stearyl Phosphate
10 parts (LBT-1830 purified, manufactured by Sakai Chemical
Industry Co., Ltd.) Zinc stearate 10 parts (SZ-PF, manufactured by
Sakai Chemical Industry Co., Ltd.) Polyethylene wax 10 parts
(POLYWAX 3000, manufactured by Toyo ADL Corp.) Filler 1 part (MICRO
ACE P-3, manufactured by Nippon Talc Co., Ltd.) methyl ethyl ketone
200 parts toluene 100 parts
Comparative Example 1
A thermal transfer sheet of Comparative Example 1 was obtained by
carrying out the same procedure in Example 1 except that the liquid
for forming back face layer 1 was replaced by a liquid for forming
back face layer A having the following composition.
<Liquid for Forming Back Face Layer A>
TABLE-US-00013 Molar equivalent ratio (--NCO/--OH): 0.52 Polyvinyl
acetal resin 52 parts (S-LEC KS-1, manufactured by Sekisui Chemical
Co., Ltd.) Polyisocyanate 18 parts (BURNOCK D750, manufactured by
DIC Corporation) Zinc stearyl Phosphate 10 parts (LBT-1830
purified, manufactured by Sakai Chemical Industry Co., Ltd.) Zinc
stearate 10 parts (SZ-PF, manufactured by Sakai Chemical Industry
Co., Ltd.) Polyethylene wax 10 parts (POLYWAX 3000, manufactured by
Toyo ADL Corp.) methyl ethyl ketone 200 parts toluene 100 parts
Comparative Example 2
A thermal transfer sheet of Comparative Example 2 was obtained by
carrying out the same procedure in Example 1 except that the liquid
for forming back face layer 1 was replaced by a liquid for forming
back face layer B having the following composition.
<Liquid for Forming Back Face Layer B>
TABLE-US-00014 Molar equivalent ratio (--NCO/--OH): 0.53 Polyvinyl
acetal resin 51.2 parts (S-LEC KS-1, manufactured by Sekisui
Chemical Co., Ltd.) Polyisocyanate 17.8 parts (BURNOCK D750,
manufactured by DIC Corporation) Silicone resin (average particle
diameter: 2 .mu.m, 1 part spherical shape) (Tospearl 120,
manufactured by Momentive Performance Materials Japan LLC) Zinc
stearyl Phosphate 10 parts (LBT-1830 purified, manufactured by
Sakai Chemical Industry Co., Ltd.) Zinc stearate 10 parts (SZ-PF,
manufactured by Sakai Chemical Industry Co., Ltd.) Polyethylene wax
10 parts (POLYWAX 3000, manufactured by Toyo ADL Corp.) methyl
ethyl ketone 200 parts toluene 100 parts
(Evaluation for Printing Residue)
Each of the thermal transfer sheets obtained in Examples 1 to 8 and
Comparative Examples 1 and 2 was in combination with a thermal
transfer image-receiving sheet for Mitsubishi Electric
Corporation's sublimation type printer (CP9800D), and underwent
printings for 0-gray scale image, 128-gray scale, and 225-gray
scale image, at printing meter numbers of 400 m, 800 m, and 1200 m,
respectively, under the following condition. The conditions of the
printing residue attached to the thermal head at these printings
were observed visually, and were evaluated according to the
following criteria. The evaluation results were shown in Table
1.
"Printing Condition"
Thermal head: head resistance 5020.OMEGA., resolution 300 dpi (dots
per inch) (manufactured by Toshiba Hokuto Electronics Co., Ltd.)
Line speed: 1 ms/Line, (The resolution in the sheet conveying
direction was 300 lpi (line per inch).) Pulse duty; 90% Applied
power: 32V Printing pressure; 40N Print image: the size was 1600
pixels in width.times.1090 pixels in length, and the images were
gradient images of 0-255 gray scale (1 pixel was correspondent to 1
dot.) "Evaluation Criteria" .circleincircle.: The printing residue
was not accumulated around heating element. .largecircle.: A trace
quantity of the printing residue was observed around the heating
element. .DELTA.: Inconsistencies in density were not observed on
the printing, although the printing residue was accumulated around
heating element. X: Inconsistencies in density were appeared on the
printing, and the printing residue was accumulated around heating
element.
Incidentally, when the evaluation is .circleincircle. or
.largecircle., it is possible to obtain a good printed matter with
little fear of causing color voids in the printed matter.
(Evaluation for Inconsistencies in Density on Printing)
Each of the thermal transfer sheets obtained in Examples 1 to 8 and
Comparative Examples 1 and 2 was in combination with a thermal
transfer image-receiving sheet for Mitsubishi Electric
Corporation's sublimation type printer (CP9800D), and underwent
printings of 255-gray scale pattern in the first half, and 180-gray
scale pattern in the second half. The obtained printings were
observed visually, and were evaluated according to the following
criteria. The evaluation results were shown in Table 1. Herein, the
printing condition used herein was the same as used in the above
mentioned evaluation for printing residue.
"Evaluation Criteria"
.largecircle.: The 180-gray scale part of the printed matter was
uniformly printed. There is no inconsistency in density on the
printed matter. .DELTA.: Inconsistencies in density were slightly
observed in the 180-gray scale part of the printed matter. X:
Inconsistencies in density were significantly observed in the
180-gray scale part of the printed matter. (Evaluation of Printing
Flaws)
Each of the thermal transfer sheets obtained in Examples 1 to 8 and
Comparative Examples 1 and 2 was in combination with a thermal
transfer image-receiving sheet for Mitsubishi Electric
Corporation's sublimation type printer (CP9800D), and underwent
printings of 255-gray scale pattern at printing meter numbers of 20
m, respectively, under the above mentioned printing condition.
Herein, the printing was performed at 0.degree. C. environment. The
obtained printings were observed visually, and were evaluated for
the printing flaws according to the following criteria. The
evaluation results were also shown in Table 1.
"Evaluation Criteria"
.largecircle.: There was no occurrence of the printing flaw.
.DELTA.: There were occurrences of printing flaws, but no tendency
to increase. X: There were occurrences of printing flaws, and the
number of occurred print flaws was increased as the number of
printing was increased.
Incidentally, when the evaluation is .largecircle., it is possible
to obtain a good printed matter with little fear of causing color
voids in the printed matter.
TABLE-US-00015 TABLE 1 Evaluation for Evaluation Evaluation for
Printing residue inconsistencies for 255-gray scale 128-grey scale
0-grey scale in density on printing 400 m 800 m 1200 m 400 m 800 m
1200 m 400 m 800 m 1200 m printing flaws Example 1 .circleincircle.
.circleincircle. .circleincircle. .circleincirc- le.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.c- ircleincircle. .largecircle. .largecircle. Example 2
.circleincircle. .circleincircle. .circleincircle. .circleincirc-
le. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .c- ircleincircle. .largecircle. .largecircle.
Example 3 .circleincircle. .circleincircle. .circleincircle.
.circleincirc- le. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .c- ircleincircle. .largecircle.
.largecircle. Example 4 .circleincircle. .circleincircle.
.circleincircle. .circleincirc- le. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .c-
ircleincircle. .largecircle. .largecircle. Example 5
.circleincircle. .largecircle. .largecircle. .circleincircle. .c-
ircleincircle. .largecircle. .circleincircle. .circleincircle.
.circleinci- rcle. .largecircle. .largecircle. Example 6
.circleincircle. .largecircle. .largecircle. .circleincircle. .c-
ircleincircle. .largecircle. .circleincircle. .circleincircle.
.circleinci- rcle. .largecircle. .largecircle. Example 7
.circleincircle. .circleincircle. .circleincircle. .circleincirc-
le. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .c- ircleincircle. .largecircle. .largecircle.
Example 8 .circleincircle. .largecircle. .largecircle.
.circleincircle. .c- ircleincircle. .largecircle. .circleincircle.
.circleincircle. .circleinci- rcle. .largecircle. .largecircle.
Comparative .DELTA. X X .largecircle. .largecircle. .DELTA.
.largecircle. - .largecircle. .largecircle. X X Example 1
Comparative .largecircle. .DELTA. X .largecircle. .largecircle.
.DELTA. .l- argecircle. .largecircle. .largecircle. .DELTA. .DELTA.
Example 2
EXPLANATION OF NUMERIC SYMBOLS
1 . . . Substrate 2 . . . Releasing layer 3 . . . Transcriptive
protective layer 4 . . . Color material layer 5 . . . Back face
layer 6 . . . Primer layer 7 . . . Heat-resistant lubricating layer
20 . . . Polygonal shaped organic minute particle 10 . . . Thermal
transfer sheet
* * * * *